Processing of wax



United States Patent PROCESSING OF WAX Miles Anthony Joanen, Houston, Tex., assignor to Sinclair Refining Company, New York, N. Y., a corporation of Maine No Drawing. Application October 26, 1949, Serial No. 123,781

2 Claims. (Cl. 26028.5)

My invention relates to a method of modifying paraffin wax and embraces as a novel composition parafiin wax which has been treated according to the method.

As employed herein, the term paraflin wax refers to the hard, crystalline wax derived from distillates obtained upon the fractionation of petroleum oils of the mixed base or parafiin base type. Separation of this wax from the distillate is conveniently effected by chilling the distillate to a temperature below 32 F. and then filtering the solid wax from the oil in a filter press. The wax collected in the filter press is identified in the art as slack wax and is characterized in that it contains a large quantity of oil. In most refineries, this oil is removed from the slack wax by sweating following a redistillation. Generally the wax is further refined as by treatment with sulfuric acid or percolation through clay, the resulting product being graded according to its properties, such as tensile strength, melting point, oil content, hardness, etc.

Parafiin wax is in extensive use by paper and container manufacturers as a coating material in the production of moisture-proof wrappers and cartons for the food and related industries. Much work has been done in an efiort to improve parafiin wax with this use in mind. A large proportion of this work has been directed toward increasing the tensile strength of the wax thereby to make practicable sealing of bread wrappers, for example, by the mere heating of overlapping seams of the waxed paper. Other work has had as its object improvement of the ductility or improvement of the gloss of the wax. Still other work has had as its object the prevention of blocking and it is with blocking, particularly, that my invention is concerned.

Blocking refers to the tendency of paraflin wax slabs or sheets of paraifin waxed paper stock to adhere to each other in stacks and it also refers to a similar tendency on the part of rolls of parafiin waxed paper.

I have discovered that polyethene is an efiective antiblocking agent when incorporated in parafiin wax and I have further found that when used in the amounts in which it is effective as an anti-blocking agent that it does not materially impair the tensile strength or any other desirable quality of the wax. In fact, by the incorporation of polyethene the hot sealing characteristics, sloughing resistance and gloss are in most instances substantially improved.

As a result of my discovery, slabs of parafiin wax can now be stored over prolonged periods, even at temperatures upwards of 100 F. without sticking and the same is true with respect to waxed paper whether stacked, or stored on rolls. My invention will be recognized as revolutionary by users of paraflin wax, particularly in southern climes, who have stored wax in the form of slabs during the summer season. No previously proposed anti-blocking agent, of which I am aware, matches my agent in effectiveness.

In the practice of my invention, a large number of polyethene compositions of varying properties may be used, but I prefer the solid granular products, particularly the polymeric products of the approximate molecular weight range of 2000 to 15,000. The higher molecular weight materials are probably effective but they are generally incompatible with the wax. In the accompanying Table I, the average properties of typical compositions are given by way of illustration. This table is not to be taken as in any way restrictive of the scope of my invention.

Table I General properties:

Specific gravity 092. Grams per cu. in 15.04. Mechanical properties:

Tensile strength (p. s. i.) 1,800.

Brittle temperature, C Below 70. Stiffness in flexure (p. s. i.), 18,000.

25 C. Elongation (percent) Electrical properties:

Volume resistivity (ohms cms.)

Greater than 10 immersion 24 hrs.). Efiect of sunlight Solubility:

Insoluble in all common solvents below 5060 C.; soluble in chlorinated solvents, aliphatic and aromatic hydrocarbons at elevated temperatures.

No discoloration.

The polyethene, of course, is customarily added to the wax with the Wax in the liquid state. I generally make the addition at a temperature of about 220 F. At this temperature the polymer readily disperses and becomes miscible upon stirring into crystalline wax. Where desired, a Wax concentrate of the polyethene may be prepared for subsequent admixing with additional quantities of wax.

The polyethene is best employed in a concentration of about 3% on the weight of the wax. Concentrations between about 1% and 5%, however, may be employed, depending somewhat upon the molecular Weight of the polymer and the nature of the wax. Smaller amounts are relatively less or completely ineffective while larger amounts not only alter the appearance and adversely affect the properties of the wax, but generally are incompatible. I have noted that concentrations of polyethylene of over 5% have a tendency to form ridges and bulges -on the' wax plain "surfaceafter'cooling,-' regard-- 7 less of the rate of cooling, whereas the surface appearance of waxes containing about weight per cent of polyethylene or less is ordinarily free of ripples. The following data of Table II further illustrate the lack of compatibility of polyethylene in paraffin wax in concentrations above about 5%. The data concern paper which was coated with wax polyethylene compositions. The coated sampleswere stored at=-=125 F. for 24 hours and ene DEM- 1865.

The DEM 1865 polymer used in the above tests was polyethylene with molecular weight of about 3700. Higher molecular weight polyethyleues .show decreasing compatibility withpar'afiiif For example, polyethylene having molec'ula'r'weight of about 20,000 is very.

difiicult to disperse in wax even in very low concentrations. Thus a temperature exceeding 200 F. is. necessary to eifect solutionof "the higher polymer in a 5 weight per cent concentrate. The odor and taste of.the wax, however, tend to go bad at suchelevated temperatures and the time consumed in "the operation is excessive.

Even. when the polymer. is carefully ground to a size of the order of 14 mesh 'using a Burr mill after mixingiwith crushed Dry Ice to prevent sticking, the timev andtemperature to effect solution in concentrations suitable for blending off are excessive. For example, when a 2 per cent blend was prepared from a 25 per cent concentrate of polyethylene 20,000 in a 130.to 132 F. melting point wax, the polymer precipitates on cooling as a light floc and upon solidification separates as small grains within the wax.

I have found in general that the hardness of the wax as measured by the Abraham consistometer at 100". F. increases with increasing amounts 'of' polyethylene... I consider that an. increase in hardness as indicated by-this test is a fairly reliable indication of a reduction in blocking tendency.

Although the tendency of a wax 'to'block 'is prevalent and .very troublesome in the practical arts, it is very diflicult to evaluate 'in' the laboratory or by means of control tests. One widely used test for blockingtendency is TAPPl'Tentative Standard T477m47. According to this procedure the blocking tendency of paper coated with wax or wax blends is tested at '75 per cent relative humidity. The following results are illustrative of thesubstautial improvement effected by adding lower molecular Weight polyethylenesto refined paraflin wax in the 1 to 5 per .centrange. It should be noted that if the. proportions of polyethylene are increased above this range, little, if any, improvement in blocking resistance is found and the. blends.no..longer.represent.homogeneous films becauseof the increasing incompatibility of .the polyethylene in the Wax above about 5 per cent concentration. The

results are reported according tothe following. quantitative scale:

-Table-III Weight Percent Polyethylene in 130l132 F. Melting Point (ASTM) Crystalline Parafiin Wax Blocking Results Tested at- F 4 2 1 1 1 3 3 l00F. 8 7 4 5 2 5 6 F 9 8 8 6 8 6 4 7 F.. 10 9. 8 '9 28- 6 7 7 7 9. 10 9 -"10 7 10 9 8 Table. IV

Weight PerceniE Tolyeth1efib DLYT (12.000 mol. wt.) in .125i127.:' F.i1Meltlng:"do1nt (ASGEM) Crystalline Wax Blocking Results Tested at 105 F- FacetoFa'ce. 6 3 2 0 1 2 "Backtd Face 2 2 1 3 2. 110""F-;- Faceto Face 7 4 3 3 V 2 'Ba'cktbFace 3 3 2 3 2' llfl i- -'Face.to.17ace-u .8 4 4 4 2 2 ".Biickto'Faee 5 2 3 3 *Difiused'into paper, noadhesion, no matting.

Although-such laboratory tests; give a reliable inrlieartiontof blocking-tendency, I' have .foundathat practical tests .011 the".- wax in. the- ;blend -.are. more expressive respect. tosthe valueof wax; polyethyleneblendszinthe range;ioflmywinventiona; For. example; ineone .plant -test 40 slabs-of; ordinary fully-refined-wax and-40. slabsfo r anti-"blocking: wax. containing 3 vper cent;polyethylene 3,700 were placed: in twoindividual stacks. The slabs.

measured 19.-inchesinlength' by. 12 inches intwidth by 1% inches in thickness and Weighed approximately. =10

pounds. .each.. Blocking: tendency was checked using. an improved chattlionspring-balance reading .from. 0 to- 50 with a pull-zof approximately 20-.poundsand two onmore slabs withea.verticalweightpull of about 35: pounds. I wasirnpossible to'releaseuone .onmore slabsaofthe fully. refined without polyethylene added 7 with- .a pull. upl

to Sit-pounds reading. The. straight-wax. slabs .hlocked excessively, and co'uldmot be shaken or, pulled apart in.)

a .pileof ahout.30oslabs. 'Bycontrast a stack..of.4 or. 5 'of the anti-blocking slabs could be easily ,re lease'dirom;

hours. Rolls .sirnilarly coated with ordinary 13.0 to 13 2"" F. waxshowed considerable penetration of a the wax into the sheet and'alsoblockedbadly.

In'other tests' waxed loaves ofbre'ad Were't'es'ted for sloughing by e'xposing'the packages to a'ternperature-of 115 I F5 automobilewith' windows closed-*out""in several hours'a Under these conditions;*fl:ie"

wax polyethylene coating did not rub 011 the wrapper at all while the ordinary wax coating sloughed very badly. I have also noticed improvements in gloss and heat sealing qualities of the wax polyethylene blends.

The efiect of adding 3 per cent polyethylene to fully refined wax having a melting point of 137 F. is illustrated in the following table:

1 Bakelite polyethylene DEM 1865 (molecular weight 3700). 1 Moisture vapor transmission rate.

Table VI, submitted in further illustration of the invention, provides a comparison between a wax modified according to the invention, the wax being a fully refined crystalline wax derived from an East Texas crude, and a specially prepared paper wax now in current use by many waxed paper manufacturers, this wax being identified in the table as Competitive wax. From this table it is to be observed that my modified wax is superior to the competitive Wax, not only in blocking resistance but also in the matter of heat seal and gloss. The coated paper used in these tests was produced by water-waxing in a paper converting plant using conventional equipment, while the heat seal performance test, as indicated, was carried out in a commercial bakery.

Table VI East Texas Modified East Com petitive Fully Texas Wax 1 ax Wax Gravity 11. 5 41. 2 41. 2. Viscosity at 210 F. (5813)---- 41 43 39. Appearance in Slab Form.-- White..- Opaque White Color, Seybolt 30 30 30.

P. (AMI 136. 2 135. 0. Tensile Strength. ill. sq. 111.- 235 260 180. California Oil, Percent 51 62 51. Acid, ASTM K- 0K OK. Penetration:

Needle at 77 F 12 11 15. Needle at 85 F 18 19 10. eedle at 25 24 22. Needle at 100 F 50 54 50. Hardness at 90 F 29. 6 28. 0 32. 6. Hardness at 100 F 14. 6 15. 3 11. 3. Tensile Strength (Tinius Ol- 23 160.

sen #11, sq. in).

Odor at 200 F..- None--- Slight None.

Dlscoloration with Ooncmdo dn Do.

trated Sulfuric Acid.

Surface Wax per Beam on 12.3 flreamnn 13.2i/ream.

Test Sheet.

Beat Seal, grams/linear inch 9. 8.2.

required to rupture seal Heat Seal, Bakery Periorm- Good Fair.

anee Test.

gloss on Pa P Exoellent.. G ood.

oughinz o aper on xeeuive. Blocking, Stub Boll Exposed rln Bad.

Oven 14 hours at 100 F. Blocking. Lost or Wrapped do Very Bad.

Bread Exposed to O oled Car in Sun 4 hours, Tempenture 116 1.

0% Bakelite WWII! DIN 1866 (mm 013M 3700).

My invention, of course, is not limited to parafiin wax as employed in the production of bread wrappers and the like as it may also be =.;tilized, for example, in the manufacture of moisture-proof paper cartons and other containers. The invention is not, in fact, limited to the paper converting industry. I have described it with particular reference to that industry merely because, at the moment, it is in that field that it appears to have the greatest commercial promise.

The polyethylene employed in the tests of Tables V and VI has a melting point (ASTM) of 200 F. and a needle penetration at 77 F. of 24.

Further examples of useful polyethylene polymers for the purpose of my invention include:

Table VII P 1 M 1. W B (it B oymer O at M. P., F

This application is a continuation-in-part of my application Serial No. 705,249, filed October 23, 1946, now abandoned, and is intended to more precisely define the nature of the polyethylene and the proportions disclosed therein.

I claim:

1. A modified paraffin wax composition of improved resistance to blocking consisting essentially of crystalline parafiin wax having incorporated therein about 3 percent polyethylene having a molecular weight of the order of 5 about 3,700.

2. A method of improving the blocking resistance of crystalline parafiin wax which comprises preparing a mix ture which consists essentially of crystalline paraifin wax having incorporated therein about 3 percent polyethylene having a molecular weight of the order of about 3,700.

References Cited in the file of this patent UNITED STATES PATENTS 5 2,504,270 MacLaren et al Apr. 18, 1950 2,551,087 Barnhart et al. May 1, 1951 OTHER REFERENCES British Plastics, May 1945, pages 213 and 214. Alkathene, Imperial Chemical Industries, November 1943, page 4.

British Plastics, March 1945, page 96. British Plastics, April 1945, pages 148-151. 

1. A MODIFIED PARAFFIN WAX COMPOSITION OF IMPROVED RESISTANCE TO BLOCKING CONSISTING ESSENTIALLY OF CRYSTALLINE PARAFFIN WAX HAVING INCOROIRATED THERIN ABOUT 3 PERCENT POLYETHYLENE HAVING A MOLECULAR WEIGHT OF THE ORDER OF ABOUT 3,700. 